Alicyclic compounds

1. Alicyclic Hydrocarbons

2. Open-chain and cyclic compounds
In the compounds that we have studied in previous chapters, the carbon atoms are
attached to one another to form chains; these are called open-chain compounds, In
many compounds, however, the carbon atoms are arranged to form rings; these are
called cyclic compounds.
In this chapter we shall take up the alicyclic hydrocarbons (aliphatic cyclic
hydrocarbons). Much of the chemistry of cycloalkanes and cycloalkenes we already
know, since it is essentially the chemistry of open-chain alkanes and alkenes.
Nomenclature
Cyclic aliphatic hydrocarbons are named by prefixing cyclo- to the name of the
corresponding open-chain hydrocarbon having the same number of carbon atoms as
the ring. For example:
Substituents on the ring are named, and their positions are indicated by numbers, the
lowest combination of numbers being used, in simple cycloalkenes and
cycloalkynes the doubly- and triply-bonded carbons are considered to occupy
positions 1 and 2. For example:

3. For convenience, aliphatic rings are often represented by simple geometric figures:
a triangle for cyclopropane, a square for cyclobutane, a pentagon for cyclopentane,
a hexagon for cyclohexane, and so on. It is understood that two hydrogens are
located at each corner of the figure unless some other group is indicated. For
example:
Polycyclic compounds in a variety of strange and wonderful shapes have been
made, and their properties have revealed unexpected facets of organic chemistry.
Underlying much of this research there has always been the challenge; can such a
compound be model

4. Industrial source
Cycloalkanes are converted by catalytic reforming into aromatic hydrocarbons, and
thus provide one of the major sources of these important compounds. For example:
so addition of hydrogen to aromatic compounds yields cyclic aliphatic compounds,
specifically cyclohexane derivatives. An important example of this is the
hydrogenation of benzene to yield pure cyclohexane.

5. As we might expect, hydrogenation of substituted benzenes yields substituted
cyclohexanes. For example cyclohexanol.
From cyclohexanol many other cyclic compounds containing a six-membered ring
can be made.
Preparation
Preparation of alicyclic hydrocarbons from other aliphatic compounds generally
involves two stages: (a) conversion of some open-chain compound into a compound
that contains a ring, a process called cyclization; (b) conversion of the cyclic
compound thus obtained into the kind of compound that we want: for example,
conversion of a cyclic alcohol into a cyclic alkene, or of a cyclic alkene into a cyclic
alkane. Very often, cyclic compounds are made by the adapting of a standard
method of preparation to the job of closing a ring. For example, that the alkyl
groups of two alkyl halides can be coupled together through conversion of one
halide into an organometallic compound (a lithium dialkylcopper) :

6. The same method applied to a tf/halide can bring about coupling between two alkyl
groups that are part of the same molecule:
Problem.1 Starting with cyclohexanol, how would you prepare:
(a) cyclohexene, (b) 3-bromocyclohexene, (c) 1,3-cyclohexadiene?
Problem.2 Bromocyclobutane can be obtained from open-chain compounds. How
would you prepare cyclobutane from it?

7. Reactions
Alicyclic hydrocarbons undergo the same reactions as their open-chain analogs.
Cycloalkanes undergo chiefly free-radical substitution For example:
Cycloalkenes undergo chiefly addition reactions, both electrophilic and free
radical; like other alkenes, they can also undergo cleavage and allylic substitution.
For example:

8. Reactions of small-ring compounds. Cyclopropane and cyclobutane
The two smallest cycloalkanes, cyclopropane and cyclobutane, show certain
chemical properties that are entirely different from those of the other members of
their family.
In each of these reactions a carbon-carbon bond is broken, and the two atoms of the
reagent appear at the ends of the propane chain:
Cyclobutane does not undergo most of the ring-opening reactions of cyclopropane; it is
hydrogenated, but only under mote vigorous conditions than those required for cyclopropane, thus
cyclobutane undergoes addition less readily than cyclopropane and, with some exceptions,
cyclopropane less readily than an alkene. The remarkable thing is that these cycloalkanes undergo
addition at all.

9. Baeyer strain theory
Thus Baeyer considered that tings smaller or larger than cyclopentane or cyclohexane were
unstable; it was because of this instability that the three- and four membered rings
underwent ring-opening reactions; it was because of this instability that great difficulty had
been encountered in the synthesis of the larger rings.
Conformations of cyclohexane that are free of angle strain
Equatorial and axial bonds in cyclohexane
Let us return to the model of the chair conformation of cyclohexane figure above. Although the
cyclohexane ring is not flat, we can consider that the carbon atoms lie roughly in a plane. If we
look at the molecule in this way, we see that the hydrogen atoms occupy two kinds of position:
six hydrogens lie in the plane, while six hydrogens lie above or below the plane.

10. Aromatic compounds are benzene and compounds that resemble benzene in chemical behavior.
Aromatic properties are those properties of benzene that distinguish it from aliphatic
hydrocarbons.

11. Besides the compounds that contain benzene rings, there are many other substances
that are called aromatic; yet some of these superficially bear little resemblance to
benzene.
Benzene molecule: shape and size
From the experimental standpoint, aromatic compounds are compounds whose
molecular formulas would lead us to expect a high degree of unsaturation, and yet
which are resistant to the addition reactions generally characteristic of unsaturated
compounds.